Anthracyclinone aglycones when combined with natural and unnatural amino sugars comprise an important class of antitumor agents. Our proposed work involves the development of novel synthetic methods for the construction of aglycones of the rhodomycinone and aklavinone classes of these anthracyclinones. The synthetic strategy involves coupling of a fully functionalized AB-ring system to a CD-ring precursor to afford the intact tetracyclic system. This requires developing chemistry which successfully joins these two fragments under very mild conditions. This approach has resulted in an excellent synthesis of 4-demethoxydaunomycinone. This chemistry will be further explored to synthesize optically active aglycones of the rhodomycinone and aklavinone classes. These compounds will then be coupled with natural and fraudulent amino sugars to obtain systems for testing, metabolism studies, and tissue distribution studies.